Process for the fast dyeing of natural and artificial polyamide fibers with water-soluble metal-containing azo dyestuffs



. o p 3, 4 ,648 Patented July 1962 (a) A mixture of a basic water-soluble polyglycol 3,043,648 ether, produced by combining ethylene oxide with a poly- PROCESS FOR THE FAST DYEING OF NATURAL p AND ARTIFICIAL POLYAMIDE FIBERS WITH ammeofthefmmula gATE ll zl-gg IUBLE METAL-CONTAINING AZO 5 (I) Hans Martin Hemmi and Albin Peter, Binningen, near h Basel, Switzerland, assignors to Sandoz Ltd., Basel, W

swltlellalld R stands for an alkyl radical which contains at least 8 N0 Drawing- F'led 195s 779,046 carbon atoms, an alkenyl radical with 8 to 18 carbon Claims Priority gf g zg fgg 195s 10 atoms, an alkylphenyl or dialkylphenyl radical which contains at least 5 carbon atoms in the alkyl group or a The present application is a continuation-in-part of 00- higher alkylpolyglycol ether radical, and pending application Ser. No. 625,594, filed December 3, R for the radical of an aliphatic di-or triamine, which 1956 (abandoned since the filing of the present applicais attached through a nitrogen-atom to the CH tion). group, and if desired by quaternating the thus obtained With the development of the synthetic nitrogenous addition product, and of a Water-soluble polyglycol fibers there has been a marked increase in the consumpether carboxylic acid of the formula tion of wool dyestuffs. There is a particularly heavy demand for water-soluble dyestuffs capable of dyeing nitros 2- 2 )x zgenous fibers such as wool, silk, mian made nitrogenous fibers of casein, and synthetic polyamide and polyure- Wherem 1113116 fibers in .shades fast to light, Washing and mining- R stands for an alkyl or alkenyl radical which contains Experience has shown that for these purposes water-solat least 1 carbon atoms or an ,alkylaryl dialkyl'aryl uble, metal-containing dyestuffs are 1116 most Suitableradical which contains more than 13 carbon atoms, and It is very difficult, however, to apply the members of these f v integer great-er than 19 dyestutf classes to the fiber so as to ensure uniform affinity and level-dyeing. Furthermore, it is recognized (b) An organic acid.

that the optimum pH value for W001 dyeing is about 4 (0) An alkali metal salt of an organic acid, which can to 5.5. Wool dyed in this pH region is well protected act as abuifer substance, and physically, and its elastic properties remain unimpaired. (d) At. least 10%, calculated on the weight of the The spinning properties, too, are favorably affected and fiber, of an alkali metal sulfate. Dyeing is carried out the goods manufactured from such dyed wools have a by adding the dyestuif solution to the dyeing liquor at a soft, lofty hand. When wool is dyed at a pH of about temperature below the boil or at boiling temperature, 4 to 5.5 without a dyeing assistant, however, the resulting dyeing being conducted at boiling temperature. Stripping dyeings are not only unlevel but also of poorfastness to is carried out by adding the dyeing to the stripping medicrocking. In view of this it has been a long-standing aim um containing the ingredients listed above at a temperaof research to establish a dyeing process whereby waterture below the boil or at boiling temperature, stripping soluble, metal-containing azo dyestufls, can be dyed from I being conducted at boiling temperature.

a weakly acid dyebath in level shades of good fastness to Under the term basic water-soluble polyglycol ethers as crocking. here defined are to be understood products such as those It has now been found that natural and artificial polyenumerated by way of example in the following Table I.

amide fibers can be dyed in the weakly acid region with They are characterized by the fundamental substance used waterasoluble metal-containing azo dyestuifs, applied for their formation, the number of mols of ethylene oxide singly or in combination with each other, to give level and reacted with the said fundamental substance, and the numfast shades and that the dyeings on natural or artificial ber of quaternated, preferably with dimethyl sulfate, nitropolyamide fibers obtained with such dyestuffs can be gen atoms. In Table II the water-soluble polyglycol stripped from the said fibers. ethercarboxylic acids are characterized by the fundamen- The natural and artificial polyamide fibers are dyed tal substance (R employed in their formation and by from or the dyeings stripped in an aqueous dye-liquor con- 5 the number of mols of ethylene oxide (x) reacted with ta mng; the said fundamental substance.

TABLE I Number Number No. 01 the of Added oi polyglycol Fundamental Substance Mols of Quaterether Ethylnated ene Nitrogen Oxide Atoms CgHn-O OHz-CHOH-CH-NzHCzH4NHC2H4NHz 8. 5 0 E CHr-CHOHCHzNHCzHiNH-CzH4N z 8. 5 012E250CH2-OHOHCH2NHO2H4NHC2H4NH2 8. 5 0 5E330CHzOHOHCHzNHC2H4NHCzH NH2 G. 7 01 E 0CH OHOHCHzNHC2H NHCzH NHa- 5. 5 0 3E350 CHZOHOHCHZNHO2H4NHC2H4NH2. 8. 5 CrsHwOCH CHOHCHzNHC2H NHCzHANH2 10 0 11350 CH2CHOHCH2NHC H4NHCzHtNHa 12 01 E350CH2OHOHCHzNHCzH4NHC2H4NH2 l4. 8 01 E350CHgCHOHCHzNHCaH4NHCzH4NHz 20 (3 11350CHzCHOHCHzNHCzH NHCzH NHz 24 013E350CHZOHOHOH2NHO2H4NHC2H4NH2 30 (3 11 0 CHZCHOHCHZNHCZHQNHOZHANHi 40 (3 311 0 CH2CHOHCHzNHCzH NHCzH4NH2 5 (31 E 0CH1CHOHCH2NHC2H NHCzH4NHz 8. 5 01311 0 CH2CHOHCH2NHCzH4NHCzH4NHz l2 0 31 1350CHzCHOHCHzNHC2H NHCzE4NHz 12 0 E350CH20HOHCHzNHC2H NHC2H4NH2 12 5 0 3E 50CH CHOHCH2NHC H NHC H4NHZ TABLE IOontinued No. of the polyglycol ether l Fundamental Substance Number Number of Added of Mols of Quater- Ethylnated ene Nitrogen Oxide Atoms was TABLE II Number d s bt Ad d d 40 No. of the polyglycol Fun amental u s ance e ethercarboxylie acid 3 -0 Mols oi Ethylene Oxides:

0191135011 2O CrzaHasO 24 C1s z5O Cm asO 40 (CaH17)2CuHaOH 40 (C9Hm)2 aHaOH. 30 OuHmC5H4OH 0 l2 25C6 4 H 40 Of the organic acids whichmay be employed in the present process, propionic, citric and, above all acet c acid rank first in interest. Alkali-metal salts of organic acids which act as bufiers are for example sodium and potassium acetate, propionate and citrate, sodium acetate being the preferred. Potassium sulfate or, preferably, sodium sulfate serve as alkali-metal sulfates, whereby an amount of 20m 40%, calculated on the weight of the fiber, is preferred.

The dyeing process is carried out by adding the dyestuif solution to the dyeing medium, into which. the natural or artificial polyamide fiher'srhave been previously entered, advantageously at about 50-60 C. The dye-bath is then heated to the boil slowly, e.'g. in the course of about 30-60 minutes, and the maten'aldyed to shade at boiling temperature, for which a further period of about 30 to 60 minutes is necessary.

. :The resulting dyeings are leveland fast to crocking. In

addition they possessthe'other'excellent properties com- 7 In comparison with existing dyeing methods the new process presents a further advantage in that it precludes smearing, the expression used to describe the streaky dyestulf precipitateson the wall of the dye vessel, a phenomenon often observed in acid dyebaths. Another merit of the present process is the fact that the dyeings do not bleed when rinsed in water, as is often the case with the known methods.

The surprisingly good results of the new process are due to a combination of three factors, by which more is accomplished than could have been predicted from the sum of their properties; namely the combination of the mixture of the basic polyglycol ether and of the polyglycol ether-carboxylic acid conforming to the present definition with the buifered acidity of the dyebath and the distinctive action which the relatively high content of alkali-metal sulfate exerts on the course of the. dyeing process. If one of these three factors is omitted, the buffer substance or the previously mentioned polyglycol ether mixture or the alkali-metal sulfate, unlevel dyeings are generally obtained.

The following examples illustrate the invention. All parts and percentages specified therein are by weight; the temperatures are in degrees centigrade.

Example 1 100 parts of a wool hank are entered into a dyebath at 50 containing 5,000 parts of water, 1.5 parts of Lan-asyn Red BL, 0.1 part of the basic polyglycol ether No. 8 and 0.9 part of the polyglycol ether oarboxylic acid No. 44, 5 parts of sodium acetate, 2 parts of 100% acetic acid and 25 parts of sodium sulfate. The dyebath is brought to the boil in the course of 50 minutes and is then boiled for a further 30 minutes. After this time 90% of the total dyestufi employed is exhausted. The resulting dyeing is level and is a very bright red in shade.

Similarly, very level red dyeings are obtained when the Lanasyn Red BL used in this example is replaced by Lanasyn Red 2GL. For the production of level yellow parts of water, 1 part of D to orange shades the following dyestuflfs are eminently suitable: Lanasyn Yellow 3GL, Lanasyn Yellow GLN, Lanasyn Yellow 2RL and Lanasyn Orange RLN.

The basic polyglycol ether No. 8 may be replaced by an equal quantity of one of the basic polyglycol ethers of Table I and the polyglycol ether carboxylic acid No. 44 by an equal amount of one of the polyglycol ether carboxylic acids Nos. 43 or 45 to 50. The resultant dyeings are level and of bright shade.

Example 2 100 parts of loose wool are dyed in a machine with circulating liquor. The dye liquor is composed of 5,000 Lanasyn Dark Violet RL, 0.1 part of the basic polyglycol ether No. 9 and 0.8 part of the polyglycol ether carboxylic acid No. 45 parts of sodium propionate, 4 parts of 100% propionic acid "and 25 parts of sodium sulfate. The liquor is brought to the boil over 50 minutes then boiled for a further 30 minutes. After this time 95% of the dyestuff initially present is exhausted. The dyeing thus obtained is level and of a bright violet shade. The basic polyglycol ether No. 9 may be replaced by one of the basic polyglycol ethers Nos. to 25 and the polyglycol ether carboxylic acid No. 45 by one of the polyglycol ether carboxylic acids Nos. 43, 44, and 46-50; the resulting dyeings show a level violet shade.

In place of Lanasyn Dark Violet RL, Lanasyn Bordeaux RL, Lanasyn Brown RL, Lanasyn Brown 3RL and Lanasyn Gray BL may be employed with equal success.

Example 3 100 parts of wool slubbing are dyed in a dyeing machine With circulating liquor. The dye liquor is made up of 5 ,000 parts of water, 2 parts of Lanasyn Yellow GLN, 0.1 part of the basic polyglycol ether No. 8 and 1 part of the polyglycol ether carboxylic acid No. 48, 5 parts of sodium acetate, 3 parts of 100% acetic acid and 25 parts of sodium sulfate. The liquor is heated to the boil in the course of 50 minutes and boiling continued for another 30 minutes. After this time 90-95% of the dyestuff employed is exhausted. A level dyeing of bright yellowish shade is obtained. 7

Instead of the basic polyglycol ether No. 8 one of the basic polyglycol ethers Nos. 5, 6, 7, 9, 10, 11, 12 and 13 may be used with the same degree of success, while the polyglycol ether carboxylic acid No. 50 may be replaced by one of the polyglycol ether carboxylic acids Nos. 43- 47, 49 and 50.

Example 4 100 parts of loose tippy dyeing wool are dyed in a machine with circulating liquor. The dye liquor consists of 5 5,000 parts of water, 0.3 part of Lanasyn Red BL, 0.6 part of Lanasyn Brown 3RL, 0.3 part of the basic polyglycol ether No. 8 and 1.2 parts of the polyglycol ether carboxylic acid No. 49, 5 parts of sodium acetate, 2.5" parts of 80% acetic acid and 25 parts of sodium sulfate. The dyeing procedure is the same as that described in Examples 1 to 3. The red-brown dyeing which is obtained shows good uniformity of shade between the fiber roots and tips.

Level red-brown dyeings are also obtained when the basic polyglycol ether No. 8 is replaced by one of the basic polyglycol ethers Nos. 5, 6, 7, 9 to 13 or 19 to 27 and the polyglycol ether carboxylic acid No. 49 by one of tghe polyglycol ether carboxylic acids Nos. 43 to-48 or 0.

circulating liquor from a dyebath containing 0.8 part of Lanasyn Red 2GL. The dyeing is produced in the manner described in Examples 1 to 4 and shaded with 0.2 part of Lanasyn Yellow GLN, this being added to the dyebath at The red-orange dyeing thus obtained is level and of bright shade.

Example 6 parts of a wool fabric are immersed in a liquor in a winch prepared with 5,000 parts of water, 2 parts of Lanasyn Red BL, 1.5 parts of the basic polyglycol ether N0. 7, 1 part of the polyglycol ether carboxylic acid No. 43, 5 parts of sodium citrate, 30 parts of a 10% aqueous solution of citric acid and 25 parts of sodium sulfate. The dye liquor is heated to the boil in the course of 50 minutes and the material dyed to shade in the way described in Examples 1 to 4. A level and bright red dyeing is obtained. 7

When the same dyestufi is dyed by the method hitherto used, i.e. from a neutral bath with the addition of 2 parts of ammonium sulfate, the dyeing turns out unlevel and appreciably duller in shade.

Example 7 100 parts of wool fabric are entered into a blind dye liquor composed of 5,000 parts of water, 0.1 part of the basic polyglycol ether No. 8 and 0.9 part of the polyglycol ether carboxylic acid No. 45, 5 parts of sodium acetate, 25 parts of sodium sulfate and 2 parts of 100% acetic acid. The wool is boiled in this bath for 15 minutes, after which time a concentrated solution of 0.5 part of Lanasyn Gray BL and 0.1 part of Lanasyn Yellow GLN is allowed to flow into the boiling bath in the course of 30minutes. After a further 30 minutes at the boil the material is. dyed to a briught, level shade. The basic polyglycol ether No. 8 may be readily replaced by one of the basic polyglycol ethers Nos. 5, 6, 7, 9, 10, 11, 12, 13 and 19 to 27 and the polyglycol ether carboxylic acid No. 45 by one of the polyglycol ether carboxylic acids Nos. 43, 44 and 46 to 50.

When the material is dyed in the same way from a neutral bath with the addition of 2 parts of ammonium sulfate but without the polyglycol ether and the buffer mixture, the dyeing turns out very unlevel.

Example 8 100 parts of a Wool fabric dyed with 2.4 parts of Lanasyn Dark Violet RL are boiled for '30 minutes in a blind dyebath containing 5000 parts of Water, 0.4 part of the basic polyglycol ether No. 10 and 3.6 parts of the polyglycol ether carboxylic acid No. 50, 5 parts of sodium acetate, 25 parts of sodium sulfate and 2 parts of 100% acetic acid. The treatment causes the dyeing to lose heavily in depth.

'The acetic acid may be omitted altogether or reduced in quantity. The basic polyglycol ether No. 10 may be replaced by another of the basic polyglycol ethers of the Table I and the polyglycol ether carboxylic acid No. 49 by another of the polyglycol ether carboxylic acids of the Table II.

Example 9 100 parts of wool fabric are dyed 1 part of Lanasyn Orange RLN under conditions which result in an unlevel dyeing. The dyed wool fabric is subsequently boiled for 30 minutes in a blind'dyebath containing 5000 parts of Water, 0.15 part of the basic polyglycol ether No. 8 and 0.85 part of the polyglycol ether carboxylic acid No. 47, 6 parts of sodium acetate, 25 parts of sodium sulfate and 2 parts of 100% acetic acid. The treatment leaves the dyeing with a markedly leveler appearance.

In place of the basic polyglycol other No. 8 one of the basic polyglycol ethers Nos. 6,7, 9 to 13, and 19 to 40 will be found equally satisfactory; the polyglycol ether carboxylic acid N0. 47 may be replaced by one of the polyglycol ether carboxylic acids Nos. 43 to 46 and 48 7 to 58. When 1 part of Lanasyn Orange RLN is added to the blind dyebath according to this invention, white wool can be dyed therewith in level orange shades.

Example 10 :100 parts, of wool are entered into adye liquor at 50 prepared with 5000 parts of Water, 2.4 parts of Lanasyn Bordeaux BL, 25 parts of sodium sulfate, 5 parts of sodium acetate, 2 parts of 100% acetic acid, 01 part of thebasic polyglycol ether No. 9, 0.45 part of the polyglycol ether carboxylic acid No. 43 and 0.45 part of the polyglycol ether carboxylic acid No. 46. The dyebath is heated to boiling temperature over a period of 45 min utes anjd dyeing continued for 6-0 minutes at 100. A fast, level dyeing of bright Bordeaux shade is obtained.

The basic polyglycol ether No. 9 can be replaced by one ofthe polyglycol ethers Nos. 5, 6, 7, 8, 10, 11, l2, l3 and 19 to 27 and the mixture of the polyglycol ether carboxylic acids Nos. 43 and 46. by a mixture of the polyglycol ether carboxylic acids of the Table II. In the foregoingexamples the number of components in the mixture of polyglycol ethers and polyglycol ether carboxylic acids can be varied as desired.

Example 11 1100 parts of a hank of nylon 66 are entered into a dye bath made up of 5000 parts of water, 2 parts of Lanasyn Brown RL, 0.1 part of the basic polyglycol ether No. 8 and 0.9 part of the polyglycol ether carboxylic acid No. 47, 3 parts of sodium acetate, 1 part of 100% acetic acid and 25 parts of sodium sulfate. The dye liquor is raised to the boil in the course of 50 minutes, and the dyebath boiled for a further 40 minutes. After this time 93% ofthe total dyestulf employed is exhausted. A fast and level brown dyeing is obtained.

When the basic polyglycol ether No. 8 is replaced by one of the basic p'olyglycol ethers Nos. 6, 7, 9, 10, 11, 12, 13, 19 to 27, and the polyglycolether carboxylic acid No. 47: by one of the polyglycol ether earboxylic acids of the Table I I, a similarly 'fast and level brown dyeing is obtained. If the dyeing is carried out in a neutral dyebath syn Red 2GL, BL, Lanasyn Bordeaux RL, Lana-syn Dark,

Violet RL, Lanasyn Brown GRL, 3RL and Lanasyn Gray BL, 2BL behave the same as, or similarly to, Lanasyn Brown RL.

Example 12 100 parts of a Perlon fabric are entered into a dyebath containing 5000 parts of water, 2 parts Lan'asyn Yellow 3GL, 0.2 port of the basic polyglycol ether No. 6 and 1 part of the polyglycol ether carboxylic acid No. 49, 3 parts of sodium acetate, 1.5 parts of 100% acetic acid and 15 parts of sodium sl llfiate. The dye liquor is brought to the boil in the course of 50 minutes and is then boiled for 40 minutes. After thistime 97%. of the dyestuff employed is exhausted. The resultant dyeing is level and bright yellow inshade.

The basic polyglycol ether No. 6 can be replaced by another basic polyglycol ether of Table I and the polyglycol ether carboxylic acid No. 49 by one of the polyglycol ether carboxylic acids Nos. 43 to 48 and 50. Polyurethane fibers are dyed in the same way.

Example 13 100 parts of a silk hank are immersed in a dye liquor at 60 composed of 5000 parts of water, 2 parts of Lanasyn Brown 3RL, 5 parts of sodium acetate, 1 part of 80% acetic acid, 0.15 part of the basic polyglycol ether ,No. 8 and 0.85 part of the polyglycol ether carboxylic acid No.

50. The temperature of the dye bath is raised over 40 minutes to during which time a solution of 10 parts of. sodium sulfate in 100. parts of water is added in small portions. Dyeing is continued for 1 5 minutes at 90, then 2 parts of 80% acetic acid are run into the bath and dyeing completed at the same temperature in 30 minutes. The dyeing thus obtained is level and bright brown.

Should 4 parts of Lanasyn Brown 3RL be used, the amount of sodium sulfate must be increased, e.g. to 15 parts, and the total amount of 80% acetic acid to e.g. 4 parts.

The basic polyglycol ether No. 8 may be replaced without disadvantage by one of the basic p'olyglycol ethers Nos. 6, 7, 9 to 13, 19 to 27, whilst the polyglycol ether carboxylic acids Nos. 43 to 49 are equally as elfective as the polyglycol ether carboxylic acid No. 50.

The dyestuffs in Example 11 can be dyed on silk, individually or in combination, by the procedure described in this example. They yield level and fast shades.

Having thus disclosed the invention, what is claimed is:

l. A process for the fast-dyeing of fibers selected from the group consisting of wool, silk, nylon and Perlon in the weakly acid region with water-soluble,1:2-metalcontaining azo dyestuffs to give level and fast shades, which comprises dyeing the said fibers in an aqueous liquor consisting essentially of (a) a mixture of (1) a basic water-soluble polyglycol ether, produced by combining' ethylene oxide with a polyamine of the formula to the adjacent C H group through a nitrogen atom,

and the radical of derivatives thereof quaternated with ,dimethyl sulfate, and (2) a water-soluble polyglycol ether carboxylic acid of the formula R --O(CH CH O) CH COOH wherein R stands for a member selected from the group consisting of C I-I alkylphenyl with 8 to 12 carbon atoms in the alkyl group thereof, and dialkylphenyl with 8 to 12 carbon atoms in the alkyl group thereof, and x stands for an integer greater than 19; (b) an organic acid; (c) an acid-binding-bulfer consisting of an alkali metal salt of an organic acid; (d) at least 10%, calculated on the weight of the fiber,v of an alkali metal sulfate and (e) water, the dyestuff solution being added to the dyeing liquor, containing all the other ingredients, at a temperature below the boil, and conducting the dyeing at boiling temperature up to C.

2. The process for the dyeing of polyamide fibers according to claim 1, wherein the dye liquor contains acetic acid, the sodium salt of acetic acid, 25 percent of sodium sulfate and. a mixture consisting of 0.1 percent of the water-soluble polyglycol ether which is the condensation product of 0 E1 OCH CHOH-CH NHC H with 12 moles of ethylene oxide, and 0.9 percent of the water-soluble polyglycol ether carboxylic acid of the formula the percent figures being calculated on the weight of the fiber.

3. The process for the fast dyeing of polyamide fibers according to claim 1, wherein the dye liquor contains acetic acid, the sodium salt of acetic acid, 25 percent of sodium sulfate and a mixture consisting of 0.15 percent of the water-soluble polyglycol ether which is the condensation product of with 12 moles of ethylene oxide, and 0.85 percent of the water-soluble polyglycol ether carboxylic acid of the formula the percent figures being calculated on the weight of the fiber.

5. The process for the fast dyeing of polyamide fibers according to claim 1, wherein the dye liquor contains acetic acid, the sodium salt of acetic acid, 25 percent of sodium sulfate and a mixture consisting of 0.1 percent of the water-soluble polyglycol ether which is the condensation product of C1 H35OCH2CHOlII-OH2NHC2H4 with 12 moles of ethylene oxide, and 0.9 percent of the water-soluble polyglycol ether carboxylic acid of the formula the percent figures being calculated on the weight of the fiber.

6. The process for the fast dyeing of polyamide fibers according to claim 1, wherein the dye liquor contains acetic acid, the sodium salt of acetic acid, 25 percent of sodium sulfate and a mixture consisting of 0.1 percent of the water-soluble polyglycol ether which is the condensation product of with 12 moles of ethylene oxide, and 1 percent of the water-soluble polyglycol ether carboxylic acid of the formula the percent figures being calculated on the weight of the fiber.

7. A process for the fast-dyeing of fibers selected from the group consisting of wool, silk, nylon and Perlon in the weakly acid region with water-soluble, 1:2-metal-containing azo dyestuffs to give level and fast shades, which comprises first introducing the said fibers in an aqueous liquor consisting essentially of (a) a mixture of (1) a basic water-soluble polyglycol ether, produced by combining ethylene oxide with a polyamine of the formula wherein R stands for a member selected from the group 5 10 contains not more than 6 carbon atoms and is connected to the adjacent --CH group through a nitrogen atom, and the radical of derivatives thereof quaternated with dimethyl sulfate, and (2) a water-soluble polyglycol ether carboxylic acid of the formula wherein R stands for a member selected from the group consisting of C H alkylphenyl with 8 to 12 carbon atoms in the alkyl group thereof, and dialkylphenyl with 8 to 12 carbon atoms in the alkyl group thereof, and x stands for an integer greater than 19; (b) an organic acid; (c) an acid-binding buffer consisting of an alkali metal salt of an organic acid; (d) at least 10%, calculated on the weight of the fiber, of an alkali metal sulfate, and (e) water, then adding the dyestuif solution to the dyeing liquor, containing all the other ingredients, at a temperature below the boil, and finally carrying out the dyeing at a boiling temperature up to C.

8. A process for the fast-dyeing of fibers selected from the group consisting of wool, silk, nylon and Perlon in the weakly acid region with water-soluble, 1:2-metalcontaining azo dyestuffs to give level and fast shades, which comprises first introducing the said fibers in an aqueous liquor consisting essentially of (a) a mixture of (1) a basic water-soluble polyglycol ether, produced by combining ethylene oxide with a polyamine of the formula wherein R stands for a member selected from the group consisting of the radical of an aliphatic diamine which contains not more than 6 carbon atoms and is connected to the adjacent -CH group through a nitrogen atom, and the radical of derivatives thereof quaternated with climethyl sulfate, and (2) a water-soluble polyglycol ether carboxylic acid of the formula wherein R stands for a member selected from the group consisting of C H alkylphenyl with 8 to 12 carbon atoms in the alkyl group thereof, and dial kylphenyl with 8 to 12 carbon atoms in the alkyl group thereof, and x stands for an integer greater than 19; (b) an organic acid; (c) an acid-binding buffer consisting of an alkali metal salt of an organic acid; (d) at least 10%, calculated on the Weight of the fiber, of an alkali metal sulfate, and (e) water, then adding the dyestufE solution to the dyeing liquor, containing all the other ingredients, at a temperature of about 50 to 60 C., and finally carrying out the dyeing at a boiling temperature up to 100 C.

References Cited in the file of this patent UNITED STATES PATENTS 2,040,796 Rittinghausen May 12, 1936 2,539,907 Hoffman Ian. 30, 1951 2,763,530 Schuetz et a1. Sept. 18, 1956 2,835,550 Laucius May 20, 1958 2,903,324 Hirsbrunner Sept. 8, 1959 OTHER REFERENCES Rayon Textile Monthly, August 1945, pp. 93-95. Bird, C. L.: The Theory and Practice of Wool Dyeing, Society of Dyes and Colourists, 1947, pp. 58-61.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 'atent No. 3,043,648 July 10, 1962 Hans Martin Hemmi et al.,

in the above numbered pat- It is hereby certified that error appears ters Patent should read as ant requiring correction and that the said Let :orrected below.

Columns 1 and 2, TABLE I, under the heading "Fundamental Substance", and opposite "1" thereof for "C H OCH -CHOH CHN2HC2H4NHC2H4NH2" read C8H17-0CH2CHOHCH2NHC2H4NHC2H4 NH2 column 6, line 33, for "briught'" read bright column 1O line 38, for "R O(CH CH O) CH COOH" read R3 o- (cn cn o) X-CH2COOH Signed and sealed this 4th of June 1963o (SEAL) Attesting Officer Commissioner of Patents 

1. A PROCESS FOR THE FAST-DYEING OF FIBERS SELECTED FROM THE GROUP CONSISTING OF WOOL, SILK, NYLON AND PERLON IN THE WEAKLY ACID REGION WITH WATER-SOLUBLE, 1:2-METALCONTAINING AZO DYESTUFFS TO GIVE LEVEL AND FAST SHADES, WHICH COMPRISES DYEING THE SAID FIBERS IN AN AQUEOUS LIQUOR CONSISTING ESSENTIALLY OF (A) A MIXTURE OF (1) A BASIC WATER-SOLUBLE POLYGLYCOL ETHER, PRODUCED BY COMBINING ETHYLENE OXIDE WITH A POLYAMINE OF THE FORMULA 